Cathode active material and secondary battery using same

ABSTRACT

Provides is a cathode active material comprising particles each containing a lithium composite oxide, a coating layer containing an ammonium phosphate compound containing a metal other than lithium. The coating layer coats each of the particles. The metal other than lithium includes at least one selected from the group consisting of manganese, nickel, and cobalt.

BACKGROUND 1. Technical Field

The present disclosure relates to a cathode active material and a secondary battery using the same.

2. Description of the Related Art

An electrolyte liquid containing a non-aqueous solvent is referred to as a non-aqueous electrolyte. In order to improve a cycle characteristic of a secondary battery comprising a non-aqueous electrolyte, it is important to suppress a side reaction involving decomposition of the non-aqueous solvent.

In order to suppress the side reaction, various improvements have been attempted on a surface of a cathode active material that may be a reaction field of the side reaction. For example, Patent Literature 1 discloses that a particle surface of a lithium composite oxide contained in the cathode active material is coated with a solid electrolyte represented by mLi_(1+x)Al_(x)Ti_(2−x)(PO₄)₃.nLiOH to suppress the side reaction.

CITATION LIST Patent Literature

-   Patent Literature 1: Japanese Patent Application Publication No.     2018-206669

SUMMARY

In a secondary battery containing a conventional cathode active material, a discharge capacity retention ratio may be significantly decreased along with repetition of a charge/discharge cycle.

The cathode active material according to one aspect of the present disclosure comprises:

particles each containing a lithium composite oxide; and

a coating layer containing an ammonium phosphate compound containing a metal other than lithium,

wherein

each of the particles is coated with the coating layer; and

the metal other than the lithium includes at least one selected from the group consisting of manganese, nickel, and cobalt.

The present disclosure provides a cathode active material that suppresses a decrease in discharge capacity retention ratio of a secondary battery.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a cathode active material according to the present embodiment.

FIG. 2 is a vertical cross-sectional view schematically showing a secondary battery containing the cathode active material of the present disclosure.

FIG. 3 is an enlarged view of the region III shown in FIG. 2.

DETAILED DESCRIPTION OF THE EMBODIMENT

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. However, the present disclosure is not limited to the following embodiments.

Embodiment of Cathode Active Material

FIG. 1 is a cross-sectional view of the cathode active material 10 according to the present embodiment. As shown in FIG. 1, the cathode active material 10 comprises a particle 1 and a coating layer 2. The coating layer 2 coats the particle 1. The coating layer 2 may coat the entire surface of the particle 1 or may partially coat the surface of the particle 1. The coating layer 2 may be in the form of a film or an island. The coating layer 2 is in direct contact with, for example, the particle 1.

The particle 1 contains a lithium composite oxide. The particle 1 may contain a lithium composite oxide as a main component. The “main component” means the most abundant component contained in the particle 1 in view of a weight ratio. The particle 1 may consist substantially of a lithium composite oxide. “Consisting essentially of a material” means excluding other components that alter the essential characteristic of the material. However, the particle 1 may contain impurities in addition to the lithium composite oxide. Since the particle 1 contains the lithium composite oxide, the cathode active material 10 can occlude and release lithium ions.

The lithium composite oxide is, for example, a metal oxide containing lithium and a transition metal. The lithium composite oxide contains, for example, at least one selected from the group consisting of nickel, cobalt, and manganese. The lithium composite oxide may contain at least one selected from the group consisting of nickel and cobalt. In other words, the lithium composite oxide may be a metal oxide containing lithium and at least one selected from the group consisting of nickel, cobalt and manganese. The lithium composite oxide may be a metal oxide containing nickel, cobalt and lithium. In the lithium composite oxide, a ratio of the number of nickel atoms to the total number of nickel, cobalt, and manganese atoms is, for example, not less than 50%.

The lithium composite oxide has, for example, a crystal structure. The crystal structure of the lithium composite oxide is not particularly limited. The lithium composite oxide has, for example, a crystal structure which belongs to a space group R-3m or C2/m. In such a lithium composite oxide, expansion and contraction of a crystal lattice generated due to charge and discharge of a secondary battery are relatively small. Therefore, the lithium composite oxide is less likely to be deteriorated in a non-aqueous electrolyte of the secondary battery. The secondary battery containing this lithium composite oxide has an excellent cycle characteristic. Further, by using the lithium composite oxide, a secondary battery in a discharged state can be assembled.

The coating layer 2 contains an ammonium phosphate compound. The coating layer 2 may contain an ammonium phosphate compound as a main component, or may substantially consist of an ammonium phosphate compound. However, the coating layer 2 may contain impurities in addition to the ammonium phosphate compound.

The ammonium phosphate compound contains a metal other than lithium. The metal other than lithium includes at least one selected from the group consisting of manganese, nickel, and cobalt. The ammonium phosphate compound contains the metal other than lithium in the form of ions. In other words, the ammonium phosphate compound contains metal ions other than lithium ions. The ammonium phosphate compound is, for example, a salt containing a phosphate ion, an ammonium ion, and the metal ion other than the lithium ion. The valence of the metal ion other than lithium ion is, for example, two or more. The metal ions having two or more valence can bind to two or more phosphate ions. Thereby, a cross-linked structure is formed with the phosphate ions. This cross-linked structure is suitable for suppressing a decrease in the discharge capacity retention ratio of the secondary battery. However, if the valence of the metal ions is more than two, the ammonium phosphate compound has a three-dimensional cross-linked structure. The three-dimensional cross-linked structure may inhibit migration of lithium ions between the lithium composite oxide and the non-aqueous solvent. In other words, the ammonium phosphate compound functions as a resistance component, and the discharge capacity of the secondary battery may be decreased. Therefore, it is preferable that the valence of the metal ions is divalent.

The ammonium ion included in the ammonium phosphate compound includes not only NH₄ ⁺ but also a primary to tertiary ammonium ion in which at least one hydrogen atom contained in NH₄ ⁺ has been substituted with a substituent. Examples of the substituent contained in the ammonium ion include a hydrocarbon group. The hydrocarbon group has, for example, one or more carbon atoms. The upper limit of the carbon number of the hydrocarbon group is not particularly limited, and is, for example, three. The hydrocarbon group may be a chain hydrocarbon group or a cyclic hydrocarbon group. The hydrocarbon group is, for example, a saturated aliphatic group. Examples of the saturated aliphatic group include a methyl group, an ethyl group, and a propyl group. The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom. In the ammonium phosphate compound, a part of the ammonium ion may be substituted with a lithium ion.

The ammonium phosphate compound may be a compound represented by the following formula (1).

Me_(x)Li_(y)(NR₄)_(z)PO₄  (1)

In the formula (1), Me is a divalent metal ion containing at least one selected from the group consisting of manganese, nickel and cobalt. The values of x, y and z satisfy the following relational formulas: 0.25≤x≤1, 0≤y<2.5, 0<z≤2.5, and z=3−2x−y. The values of x, y and z may satisfy the following relational formulas: 0.25≤x<1, 1<y<2.5, and 0<z<1.5. The plurality of Rs are each independently a hydrogen atom or a saturated aliphatic group represented by a composition formula C_(α)H_(β)F_(γ). In this saturated aliphatic group, α, β and γ are integers satisfying the following relational formulas: α≥1, β≥0, γ≥0, and β+γ=2α+1. In the formula (1), all of Rs may be hydrogen atoms.

In the formula (1), the value of z can be identified, for example, by the following method. First, the cathode active material 10 is subjected to a thermogravimetric gas chromatography-mass spectrometry measurement (hereinafter, referred to as TG-GC/MS measurement). In the TG-GC/MS measurement, the ammonium phosphate compound contained in the cathode active material 10 is thermally decomposed to generate an NH₃ gas. By quantitatively analyzing the NH₃ gas, the amount of ammonium ions contained in the ammonium phosphate compound can be identified. The amount of the ammonium ions may be determined based on the value provided by performing the TG-GC/MS measurement of the cathode active material 10 five times. Next, the amount of phosphate ions contained in the ammonium phosphate compound is identified. The amount of the phosphate ions contained in the ammonium phosphate compound can be identified by, for example, an inductively coupled plasma (ICP) emission spectroscopy. The value of z can be calculated based on the amount of the ammonium ions and the amount of the phosphate ions contained in the ammonium phosphate compound.

The value of y in the formula (1) is varied, depending on, for example, a ratio of the weight of the ammonium phosphate compound contained in the coating layer 2 to the weight of the lithium composite oxide contained in the particle 1. As the ratio is lower, the value of y tends to be increased. On the other hand, as the ratio is higher, the value of y tends to be decreased. The value of y may be varied, depending on a condition and a surrounding environment when the coating layer 2 of the cathode active material 10 is produced.

A ratio A of the weight of the ammonium phosphate compound contained in the coating layer 2 to the weight of the lithium composite oxide contained in the particle 1 is not particularly limited. The ratio A may be more than 0.5 wt %, and may be not less than 1.0 wt % from the viewpoint of sufficiently suppressing a side reaction between the lithium composite oxide and the non-aqueous solvent contained in the secondary battery. However, if the ratio A is too high, migration of the lithium ions between the lithium composite oxide and the non-aqueous solvent may be inhibited. In other words, if the ratio A is too high, the ammonium phosphate compound functions as a resistance component, and the discharge capacity of the secondary battery may be decreased. Therefore, the ratio A may be not more than 2.0 wt %. The ratio A may be not less than 1.0 wt % and not more than 2.0 wt %.

The shape of the cathode active material 10 is, for example, particulate. As used herein, the term “particulate” includes shapes of a sphere, an ellipsoid, a scale, and a fiber. The average particle size of the cathode active material 10 is, for example, not less than 5 μm and not more than 50 μm. The average particle size of the cathode active material 10 means a particle size (D50) which corresponds to a cumulative volume percentage of 50% in a particle size distribution measured by a laser diffraction scattering method.

The cathode active material 10 can be produced, for example, by the following method. First, a salt of a weak acid containing the metal ion other than the lithium ion is prepared. An example of the salt of the weak acid is an organic acid salt. An example of the organic acid salts is acetate. Next, ammonium phosphate represented by the following formula (2) is prepared. In the expression (2), the plurality of Rs has been defined for the formula (1).

(NR₄)₃PO₄  (2)

Next, a solution containing the ammonium phosphate represented by the formula (2) and the salt of the weak acid is prepared. An example of a solvent of the solution is water. In the solution, a part of the ammonium ions included in the ammonium phosphate is exchanged for the metal ions which are other than the lithium ions and are included in the salt of the weak acid. In this way, an ammonium phosphate compound containing the metal ion other than the lithium ion is formed. Next, the solution is applied to the particle 1. For example, the solution can be applied to the particle 1 by mixing the solution and the particle 1. Next, the cathode active material 10 can be produced by drying the particle 1 to which the solution has been applied.

In a secondary battery containing a conventional cathode active material, a side reaction between the lithium composite oxide contained in the cathode active material and the non-aqueous solvent contained in the non-aqueous electrolyte proceeds during the charge of the secondary battery. Specifically, as the cathode potential is increased due to the charge of the secondary battery, the reductant ability of the lithium composite oxide is raised. Thereby, the transition metal contained in the lithium composite oxide is reduced and eluted into the non-aqueous electrolyte. On the other hand, in the non-aqueous electrolyte, a part of the non-aqueous solvent is oxidized and decomposed.

On the other hand, in the cathode active material 10 of the present embodiment, the surface of the particle 1 is provided with insulation by the ammonium phosphate compound contained in the coating layer 2. The coating layer 2 prevents (namely, suppresses) the transition metal contained in the lithium composite oxide from being reduced and eluted. In particular, the coating layer 2 can also prevent (namely, suppress) nickel, cobalt, and manganese, which are easily eluted from the lithium composite oxide into the non-aqueous electrolyte, from being eluted. Since the transition metal (e.g., nickel, cobalt, and manganese) is prevented from being reduced and eluted, the oxidative decomposition of the non-aqueous solvent is also suppressed. By suppressing the oxidative decomposition of the non-aqueous solvent, a decrease in the discharge capacity retention ratio of the secondary battery is suppressed. Thus, the cathode active material 10 of the present embodiment improves the cycle characteristic of the secondary battery. Furthermore, the cathode active material 10 of the present embodiment is suitable to improve the discharge capacity of the secondary battery.

Embodiment of Secondary Battery

FIG. 2 is a vertical cross-sectional view schematically showing the secondary battery 100 comprising the cathode active material of the present disclosure. As shown in FIG. 2, the secondary battery 100 is a cylindrical battery comprising a cylindrical battery case, a rolled electrode group 14, and a non-aqueous electrolyte (not shown). The electrode group 14 is stored in the battery case and is in contact with the non-aqueous electrolyte.

The battery case is composed of a case body 15 that is a bottomed cylindrical metal container, and a sealing body 16 that seals an opening of the case body 15. A gasket 27 is disposed between the case body 15 and the sealing body 16. The gasket 27 ensures the sealing of the battery case. In the case body 15, insulating plates 17 and 18 are respectively disposed at both ends of the electrode group 14 in a rolling axis direction of the electrode group 14.

The case body 15 has, for example, a recess portion 21. The recess portion 21 can be formed by partially pressing the side wall of the case body 15 from the outside thereof. The recess portion 21 may be formed in an annular shape along the circumferential direction of an imaginary circle defined by the case body 15 on the side wall of the case body 15. In this case, the sealing body 16 is supported by a surface of an upper part of the recess portion 21, for example.

The sealing body 16 comprises a filter 22, a lower valve body 23, an insulation member 24, an upper valve body 25, and a cap 26. In the sealing body 16, these members are stacked in this order. The sealing body 16 is attached to the opening of the case body 15 in such a manner that the cap 26 is located outside the case body 15 and that the filter 22 is located inside the case body 15.

Each of the above members forming the sealing body 16 is, for example, disk-shaped or ring-shaped. The above members other than the insulation member 24 are electrically connected to each other.

The electrode group 14 has a cathode 11, an anode 12, and a separator 13. Each of the cathode 11, the anode 12, and the separator 13 is strip-shaped. The width directions of the strip-shaped cathode 11 and the anode 12 are parallel to the rolling axis of the electrode group 14, for example. The separator 13 is disposed between the cathode 11 and the anode 12. The cathode 11 and the anode 12 are rolled spirally in a state where a separator 13 is provided between these electrodes.

When the cross section of the secondary battery 100 in the direction perpendicular to the rolling axis of the electrode group 14 is observed, the cathode 11 and the anode 12 are stacked alternately in a radial direction of an imaginary circle defined by the case body 15 in a state where the separator 13 is provided between these electrodes.

The cathode 11 is electrically connected to the cap 26 that doubles as a cathode terminal through a cathode lead 19. One end of the cathode lead 19 is connected to, for example, the vicinity of the center of the cathode 11 in the length direction of the cathode 11. The cathode lead 19 extends through a through hole formed in the insulating plate 17 from the cathode 11 to the filter 22. The other end of the cathode lead 19 is welded onto, for example, the lower surface of the filter 22.

The anode 12 is electrically connected to the case body 15 that doubles as an anode terminal via an anode lead 20. One end of the anode lead 20 is connected to, for example, the end of the anode 12 in the length direction of the anode 12. The other end of the anode lead 20 is welded onto, for example, the inner bottom surface of the case body 15.

Hereinafter, the configuration of the secondary battery 100 will be specifically described. In the secondary battery 100 of the present embodiment, known materials can be used without particular limitation, except for the cathode active material.

[Cathode 11]

FIG. 3 is an enlarged view of the region III shown in FIG. 2. As shown in FIG. 3, the cathode 11 has, for example, a cathode current collector 30 and a cathode mixture layer 31. Each of the cathode current collector 30 and the cathode mixture layer 31 has, for example, strip-shaped. The cathode current collector 30 has, for example, a pair of principal surfaces which face each other. The “principal surface” means a surface having the widest area of the cathode current collector 30. The cathode mixture layer 31 is formed on, for example, the cathode current collector 30, and is disposed on the surface of the cathode current collector 30. For example, the cathode current collector 30 is in direct contact with the cathode mixture layer 31. As shown in FIG. 3, in the cathode 11, two cathode mixture layers 31 may be formed on the pair of the principal surfaces of the cathode current collector 30, respectively. However, in the cathode 11, only one cathode mixture layer 31 may be formed on one principal surface of the cathode current collector 30. In the cathode 11, the cathode mixture layer 31 may be formed only on one principal surface of the cathode current collector 30 in at least one selected from the group consisting of the region connected to the cathode lead 19 and the region which does not face the anode 12.

Examples of the material of the cathode current collector 30 include a metal material. Examples of the metal material include stainless steel, iron, copper, and aluminum.

The cathode mixture layer 31 contains the above-described cathode active material as an essential component. The cathode mixture layer 31 may contain the cathode active material as a main component. The content ratio of the cathode active material in the cathode mixture layer 31 is, for example, not less than 80 wt % and not more than 99.5 wt %. The cathode mixture layer 31 may further contain at least one selected from the group consisting of a conductive material and a binder as an optional component. The cathode mixture layer 31 may contain an additive other than the conductive material and the binder, if necessary.

The conductive material includes, for example, a carbon material. Examples of the carbon material include carbon black, carbon nanotube, and graphite. Examples of the carbon black include acetylene black and ketjen black. The cathode mixture layer 31 may contain one or more kinds of the conductive materials. Examples of the binder include fluororesin, polyacrylonitrile resin, polyimide resin, acrylic resin, polyolefin resin, and rubbery polymer. Examples of the fluororesin include polytetrafluoroethylene and polyvinylidene fluoride. The cathode mixture layer 31 may contain one or more kinds of the binders.

A layer containing a conductive carbon material may be disposed between the cathode current collector 30 and the cathode mixture layer 31, if necessary. Examples of the carbon material include the materials described above for the conductive material.

The cathode 11 can be produced, for example, by the following method. First, a slurry containing the material of the cathode mixture layer 31 and a dispersion medium is prepared. As the dispersion medium, at least one selected from the group consisting of water and an organic medium can be used. Next, the slurry is applied to the surface of the cathode current collector 30 to provide a film. The cathode 11 can be produced by drying the provided film, and then, pressing it with a roller. If the cathode 11 has a layer containing the carbon material, the layer containing the carbon material is produced prior to the production of the cathode mixture layer 31. The layer containing the carbon material can be produced, for example, by the following method. First, a dispersion liquid containing the carbon material is prepared. The dispersion liquid is applied to the surface of the cathode current collector 30 to provide a film. The provided film is dried to produce the layer containing the carbon material.

[Anode 12]

The anode 12 comprises an anode current collector 40. As shown in FIG. 3, in the secondary battery 100 in a discharged state, the anode 12 is composed only of the anode current collector 40, for example. At this time, the secondary battery 100 is easy to ensure a high volume energy density. In the present disclosure, the discharged state means a state where the secondary battery 100 has been discharged until a state of charge (i.e., SOC) of the secondary battery 100 reaches not more than 0.05×C (where C is defined as a rated capacity of the secondary battery 100). The discharged state means a state, for example, that the secondary battery 100 has been discharged until the voltage of the secondary battery 100 reaches a lower limit voltage thereof at a constant current of 0.05 C. The lower limit voltage of the secondary battery 100 is, for example, 2.5V.

The anode current collector 40 is usually composed of a conductive sheet. The material of the anode current collector 40 may be a metal material such as a metal or an alloy. Examples of the metal material include a lithium metal and a lithium alloy. The anode current collector 40 may be composed of a lithium metal or a lithium alloy. The metal material may be a material that does not react with lithium. Such materials include materials that do not react with at least one selected from the group consisting of a lithium metal and lithium ions. More specifically, the metal material may be a material that does not form an alloy or an intermetallic compound with lithium. Examples of such metal materials include copper, nickel, iron, and alloys containing these metal elements. The alloy may be a copper alloy or stainless steel. From the viewpoint of having high conductivity and easily improving the capacity and charge/discharge efficiency of the secondary battery 100, the metal material may be copper or an alloy thereof. The anode current collector 40 may contain one or more kinds of these metal materials. The anode current collector 40 may contain a conductive material other than the metal material.

As the anode current collector 40, a foil or a film is used. The anode current collector 40 may be porous. From the viewpoint of easily ensuring high conductivity, the anode current collector 40 may be a metal foil (e.g., a metal foil containing copper). Examples of the metal foil containing copper are a copper foil and a copper alloy foil. The copper content ratio in the metal foil may be not less than 50 wt %, or not less than 80 wt %. In particular, the metal foil may be a copper foil containing substantially only copper as a metal. The anode current collector 40 has a thickness of, for example, not less than 5 μm and not more than 20 μm.

In the secondary battery 100 in the discharged state, if the anode 12 is composed only of the anode current collector 40, a lithium metal is deposited on the anode 12 when the secondary battery 100 is charged. Specifically, when the secondary battery 100 is charged, lithium ions contained in the non-aqueous electrolyte receive electrons from the anode 12. As a result, the lithium ions are changed into a lithium metal and the lithium metal is deposited on the anode current collector 40. The lithium ions contained in the non-aqueous electrolyte may be ions derived from a lithium salt added to the non-aqueous electrolyte, or may be ions supplied from the cathode active material by charging the secondary battery 100. The lithium ions contained in the non-aqueous electrolyte may be a mixture of the ions derived and supplied therefrom. The deposited lithium metal is changed into lithium ions by the discharge of the secondary battery 100 and is dissolved in the non-aqueous electrolyte.

In the secondary battery 100 in a discharged state, the anode 12 may further comprise an anode active material layer disposed on the surface of the anode current collector 40. The anode active material layer contains an anode active material. As the anode active material, an anode active material used for a known lithium ion battery can be used. Examples of the anode active material include a lithium metal, a lithium alloy, and a material capable of reversibly occluding and releasing lithium ions. Examples of the lithium alloy include a lithium-aluminum alloy.

Examples of the material capable of reversibly occluding and releasing the lithium ions include a carbon material and an inorganic material. Examples of the carbon material include graphite, soft carbon, hard carbon, and amorphous carbon. The inorganic material includes, for example, at least one selected from the group consisting of silicon and tin. Examples of the inorganic material include a silicon simple substance, a silicon alloy, a silicon compound, a tin simple substance, a tin alloy, and a tin compound. Each of the silicon compound and the tin compound may be at least one selected from the group consisting of an oxide thereof and a nitride thereof.

The anode active material layer may further contain a binder. As the binder, the material described above for the cathode mixture layer 31 can be used. The anode active material layer may further contain at least one selected from the group consisting of a conductive agent, a thickener, and another additive in addition to the anode active material and the binder. The thickness of the anode active material layer is not particularly limited, and is, for example, not less than 30 μm and not more than 300 μm in the secondary battery 100 which is in the discharged state.

A method for forming the anode active material layer is not particularly limited. The anode active material layer can be produced, for example, by depositing the anode active material on the surface of the anode current collector 40 using a vapor phase method such as an electrodeposition method or a vapor deposition method. The anode active material layer can also be produced by applying an anode mixture containing the anode active material and the binder to the surface of the anode current collector 40. The anode mixture may contain a material other than the anode active material and the binder, if necessary.

If the anode active material layer contains a material capable of occluding and releasing lithium ions, the anode active material layer occludes lithium ions during the charge of the secondary battery 100. Next, during the discharge of the secondary battery 100, the anode active material layer releases the lithium ions.

The anode 12 may further comprise a protection layer. The protection layer is formed, for example, on the surface of the anode current collector 40. If the anode 12 has the anode active material layer, the protection layer may be formed on the surface of the anode active material layer. The protection layer allows the reaction on the surface of the anode 12 to proceed more uniformly. For example, the protection layer facilities the lithium metal to be deposited further uniformly on the anode 12.

As the material for the protection layer, a material that does not inhibit the conduction of the lithium ions is used. The protection layer is composed of, for example, at least one selected from the group consisting of an organic material and an inorganic material. Examples of the organic material include a polymer having lithium ion conductivity. Examples of such a polymer include polyethylene oxide and polymethyl methacrylate. Examples of the inorganic material include ceramics and a solid electrolyte. Examples of the material of the ceramics include SiO₂, Al₂O₃ and MgO.

The solid electrolyte forming the protection layer is not particularly limited. Examples of the solid electrolyte include a sulfide solid electrolyte, a phosphoric acid solid electrolyte, a perovskite solid electrolyte, and a garnet solid electrolyte. From the viewpoint of relatively low cost and easy availability, it is preferable that the solid electrolyte is at least one selected from the group consisting of a sulfide solid electrolyte and a phosphoric acid solid electrolyte.

The sulfide solid electrolyte is not particularly limited, as long as the sulfide solid electrolyte is a solid electrolyte containing a sulfur component and having lithium ion conductivity. The sulfide solid electrolyte may contain, for example, S, Li, and other elements other than these. Examples of the other elements include at least one selected from the group consisting of P, Ge, B, Si, I, Al, Ga, and As. Examples of the sulfide solid electrolyte include Li₂S—P₂S₅, 70Li₂S-30P₂S₅, 80Li₂S-20P₂S₅, Li₂S—SiS₂, and LiGe_(0.25)P_(0.75)S₄.

The phosphoric acid solid electrolyte is not particularly limited, as long as the phosphoric acid solid electrolyte is a solid electrolyte containing a phosphoric acid component and having lithium ion conductivity. Examples of the phosphoric acid solid electrolyte are Li_(1+X)Al_(X)Ti_(2−X)(PO₄)₃ and Li_(1+X)Al_(X)Ge_(2−X)(PO₄)₃. In the composition formula, the mathematical formula 0<X<2 is satisfied. The mathematical formula 0<X≤1 may be satisfied. An example of Li_(1+X)Al_(X)Ti_(2−X)(PO₄)₃ is Li_(1.5)Al_(0.5)Ti_(1.5)(PO₄)₃.

[Separator 13]

The separator 13 has, for example, properties of ion permeability and electrical insulation. For example, a porous sheet is used as the separator 13. Examples of the separator 13 include a microporous film, a woven fabric, and a nonwoven fabric. The material of the separator 13 is not particularly limited, and may be a polymer material.

Examples of the polymer material include olefin resin, polyamide resin, and cellulose. The olefin resin may contain a polymer containing, as a monomer unit, at least one selected from the group consisting of ethylene and propylene. This polymer may be a homopolymer or a copolymer. Examples of this polymer include polyethylene and polypropylene.

The separator 13 may further contain an additive in addition to the polymer material, if necessary. An example of the additive is an inorganic filler.

[Non-Aqueous Electrolyte]

The non-aqueous electrolyte contains a non-aqueous solvent and a lithium salt. The lithium salt is dissolved in the non-aqueous solvent. The non-aqueous solvent is not particularly limited. Examples of the non-aqueous solvent include a cyclic carbonate ester, a chain carbonate ester, a cyclic carboxylic acid ester, a chain carboxylic acid ester, a chain ether, and a chain nitrile. Cyclic carbonate ester, chain carbonates ester, and carboxylic acid esters are compounds that are easily oxidatively decomposed. For the cathode active material of the present embodiment, a non-aqueous solvent containing a compound that is easily oxidatively decomposed can be used.

Examples of the cyclic carbonate ester include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate, and derivatives in which a part of hydrogen atoms contained in these compounds has been substituted with a fluoro group. Examples of the derivative having the fluoro group include fluoroethylene carbonate and trifluoropropylene carbonate.

Examples of the chain carbonate ester include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and derivatives in which a part of hydrogen atoms contained in these compounds has been substituted with a fluoro group. Examples of the derivative having the fluoro group include fluorodimethyl carbonate and trifluoroethyl methyl carbonate.

Examples of the cyclic carboxylic acid ester include γ-butyrolactone, γ-valerolactone, and derivatives in which a part of hydrogen atoms contained in these compounds has been substituted with a fluoro group.

Examples of the chain carboxylic acid ester include methyl acetate, ethyl acetate, propyl acetate, methyl dimethyl acetate, methyl trimethyl acetate, methyl propionate, ethyl propionate, propyl propionate, and derivatives in which a part of hydrogen atoms contained in these compounds has been substituted with a fluoro group. Examples of the derivative having the fluoro group include trifluoroethyl acetate and methyl trifluoropropionate.

The non-aqueous solvent may contain one or more kinds of the above compounds.

Examples of the lithium salts include LiClO₄, LiBF₄, LiPF₆, LiN(SO₂F)₂, LiN(SO₂CF₃)₂, a lithium bis(oxalate) borate (abbreviated as LiBOB), and a lithium difluoro(oxalate) borate (abbreviated as LiDFOB). The lithium salt may include at least one selected from the group consisting of, for example, LiBF₄, LiPF₆, LiN(SO₂CF₃)₂, LiN(SO₂F)₂, LiBOB, and LiDFOB. From the viewpoint of further improving the ionic conductivity of the non-aqueous electrolyte, the lithium salt may contain at least one selected from the group consisting of LiBF₄, LiPF₆, LiN(SO₂F)₂, and LiDFOB. The concentration of the lithium salt in non-aqueous electrolyte is not specifically limited, and is, for example, not less than 0.5 mol/L and not more than 3.5 mol/L.

The non-aqueous electrolyte may further contain an additive. A film may be formed on the anode 12 with the additive. By forming the film derived from the additive on the anode 12, the charge/discharge reaction of the secondary battery 100 easily proceeds more uniformly. As a result, in the secondary battery 100, a high discharge capacity is ensured, and the decrease in the cycle characteristic is further suppressed. Examples of such additives include vinylene carbonate, fluoroethylene carbonate, and vinyl ethylene carbonate. The additive may contain one or more kinds of these compounds.

[Others]

In the present disclosure, the cylindrical secondary battery 100 comprising a cylindrical battery case has been described. However, the secondary battery 100 of the present embodiment is not limited to the above. The secondary battery 100 may be, for example, a prismatic battery including a rectangular battery case or a stacking structure battery comprising an outer package such as a stacking structure sheet containing aluminum. The outer package of the stacking structure battery may contain a resin. Similarly, the electrode group 14 does not have to be rolled-shaped. The electrode group 14 may be a stacked electrode group in which a plurality of cathodes and a plurality of anodes are alternately stacked via separators.

EXAMPLES

Hereinafter, the embodiment of the present disclosure will be described more specifically on the basis of the following examples. However, the present disclosure is not limited to the following examples.

Comparative Examples 1 to 2 and Inventive Examples 1 to 48

[Production of Secondary Battery]

A secondary battery having the structure shown in FIG. 2 was produced by the following procedure.

(1) Cathode Active Material

First, particles each formed of a lithium composite oxide represented by Li_(1.2)Ni_(0.133)Co_(0.133)Mn_(0.533)O₂ were prepared. In the comparative examples 1 to 2, the particles were used as a cathode active material. In the inventive examples 1 to 48, each of the particles used in the comparative examples 1 to 2 was coated with an ammonium phosphate compound. In the inventive examples 1 to 48, each of the particles was coated with an ammonium phosphate compound by the following method. First, an acetate containing a metal ion other than a lithium ion was prepared. Triammonium phosphate and the acetate were dissolved in pure water in such a manner that a molar ratio of the acetate to the triammonium phosphate was adjusted to the value shown in Tables 1 to 2. In this way, an aqueous solution was prepared. In the aqueous solution, a part of the ammonium ions included in the triammonium phosphate was exchanged for the metal ions other than lithium ions, and an ammonium phosphate compound represented by the above-described formula (1) was formed. The values of x of the formula (1) for 48 kinds of ammonium phosphate compounds of the inventive examples 1 to 48 are shown in Tables 1 to 2. Next, the aqueous solution of the ammonium phosphate compound and the lithium composite oxide particles were added to an agate mortar and kneaded in such a manner that the ratio A of the weight of the ammonium phosphate compound to the weight of the lithium composite oxide in the provided cathode active material was adjusted to the value shown in Tables 1 to 2. At this time, the water contained in the ammonium phosphate compound aqueous solution was evaporated, and ammonium phosphate compound was precipitated. Thereby, each of the particles of the lithium composite oxide was coated with the ammonium phosphate compound. The provided particles were dried at 105° C. for 12 hours under vacuum to provide the cathode active material.

(2) Cathode

The cathode active material provided in the above section (1), acetylene black as a conductive material, and polyvinylidene fluoride as a binder were mixed at a mass ratio of 100:3:1. An appropriate amount of N-methyl-2-pyrrolidone was added to the provided mixture as a dispersion medium. A cathode mixture slurry was prepared by stirring the mixture and the dispersion medium.

Next, aluminum foil was prepared as a cathode current collector. The cathode mixture slurry was applied to both of a pair of principal surfaces of the aluminum foil. The provided coating films were dried to provide a dried product. Next, the dried product was pressed in the thickness direction of the dried product using a roller. In this way, a stacking structure was provided. By cutting the provided stacking structure into a predetermined size, a cathode having cathode mixture layers on both of the pair of the principal surfaces of the cathode current collector was provided. The cathode mixture layers were not formed in a part of the principal surfaces of the cathode current collector. In the part where the cathode mixture layers were not formed, the part of the cathode current collector was exposed to the outside thereof. In the part, one end of a cathode lead formed of aluminum was attached to the cathode current collector by welding.

(3) Anode

An anode was produced by cutting electrolytic copper foil having a thickness of 12 μm into a predetermined size.

(4) Non-Aqueous Electrolyte

First, a non-aqueous solvent and a lithium salt shown in Tables 1 to 2 were prepared. The non-aqueous solvent was a mixture of two compounds. Tables 1 to 2 also show a volume ratio of the two compounds in the non-aqueous solvent. Next, the lithium salt was dissolved in a non-aqueous solvent to provide a liquid non-aqueous electrolyte. The concentration of the lithium salt in the non-aqueous electrolyte was 1.0 mol/L. The non-aqueous solvent and the lithium salt shown in Tables 1 to 2 are as follows.

Non-Aqueous Solvent

(a) FEC: fluoroethylene carbonate

(b) DMC: dimethyl carbonate

(c) MA: methyl acetate

Lithium Salt

(d) LiPF₆: lithium hexafluorophosphate

(e) LiFSI: lithium bissulfonylimide

(5) Secondary Battery

In an inert gas atmosphere, the cathode provided in the section (2) and the anode provided in the section (3) were stacked so as to provide a separator between the cathode and the anode. As the separator, a polyethylene microporous film was used. Specifically, the cathode, the separator, the anode, and another separator were stacked in this order to provide a stacking structure. The provided stacking structure was rolled spirally to provide an electrode group. The provided electrode group was inserted into a bag-shaped outer package. The outer package was composed of a stacking structure sheet having an Al layer. Next, a non-aqueous electrolyte was injected into the outer package, and the outer package was sealed. In this way, the secondary batteries of the comparative examples 1 to 2 and the inventive examples 1 to 48 were provided.

[Evaluation of Secondary Battery]

Each of the provided secondary batteries was subjected to a charge/discharge test in accordance with the following procedure to evaluate a discharge capacity and a cycle characteristic of each of the secondary batteries.

First, the secondary battery was charged in a constant temperature bath maintained at 25° C. Next, the secondary battery was left at rest for 20 minutes, and then, the secondary battery was discharged. The conditions for charging and discharging the secondary battery are as follows.

(Charge)

First, a constant current charge was performed at a current of 10 mA per square centimeter of an electrode area. The constant current charge was performed until the battery voltage of the secondary battery reached 4.7V. Next, a constant voltage charge was performed at a voltage of 4.7V. The constant voltage charge was performed until the current value per square centimeter of the electrode area reached 1 mA.

(Discharge)

A constant current discharge was performed at a current of 10 mA per square centimeter of the electrode area. The constant current discharge was performed until the battery voltage of the secondary battery reached 2.5V.

The above charge and discharge are defined as one cycle. In the charge/discharge test, the above charge and discharge were performed for 20 cycles. The discharge capacity of the secondary battery in the first cycle is defined as an initial discharge capacity. The ratio of the discharge capacity of the secondary battery at the 20th cycle to the initial discharge capacity is defined as a discharge capacity retention ratio (%). The discharge capacity retention ratio can be used as an index of the cycle characteristic of the secondary battery. Tables 1 to 2 show evaluation results of the secondary batteries of the comparative examples 1 to 2 and the inventive examples 1 to 48. Tables 1 to 2 also show the non-aqueous solvent, the lithium salt, and the concentration of the lithium salt used for the non-aqueous electrolyte.

TABLE 1 Metal Molar ratio Value other (Acetate/ of x in Ratio Non- than Triammonium Formula A aqueous Lithium phosphate) (1) (wt %) solvent Comparative — — — 0 FEC/DMC Example 1 2/8 (v/v) Comparative — — — 0 FEC/MA Example 2 2/8 (v/v) Inventive Manganese 1/2 0.5 1.0 FEC/DMC Example 1 2/8 (v/v) Inventive Manganese 1/2 0.5 1.5 FEC/DMC Example 2 2/8 (v/v) Inventive Manganese 1/2 0.5 1.8 FEC/DMC Example 3 2/8 (v/v) Inventive Manganese 1/2 0.5 2.0 FEC/DMC Example 4 2/8 (v/v) Inventive Manganese 1/2 0.5 1.0 FEC/MA Example 5 2/8 (v/v) Inventive Manganese 1/2 0.5 1.0 FEC/DMC Example 6 2/8 (v/v) Inventive Manganese 1/1 1.0 1.0 FEC/DMC Example 7 2/8 (v/v) Inventive Manganese 1/1 1.0 1.5 FEC/DMC Example 8 2/8 (v/v) Inventive Manganese 1/1 1.0 1.8 FEC/DMC Example 9 2/8 (v/v) Inventive Manganese 1/1 1.0 2.0 FEC/DMC Example 10 2/8 (v/v) Inventive Manganese 1/1 1.0 1.0 FEC/MA Example 11 2/8 (v/v) Inventive Manganese 1/1 1.0 1.0 FEC/DMC Example 12 2/8 (v/v) Inventive Manganese 1/4 0.25 1.0 FEC/DMC Example 13 2/8 (v/v) Inventive Manganese 1/4 0.25 1.5 FEC/DMC Example 14 2/8 (v/v) Inventive Manganese 1/4 0.25 1.8 FEC/DMC Example 15 2/8 (v/v) Inventive Manganese 1/4 0.25 2.0 FEC/DMC Example 16 2/8 (v/v) Inventive Manganese 1/4 0.25 1.0 FEC/MA Example 17 2/8 (v/v) Inventive Manganese 1/4 0.25 1.0 FEC/DMC Example 18 2/8 (v/v) Inventive Nickel 1/2 0.5 1.0 FEC/DMC Example 19 2/8 (v/v) Inventive Nickel 1/2 0.5 1.8 FEC/DMC Example 20 2/8 (v/v) Inventive Nickel 1/2 0.5 2.0 FEC/DMC Example 21 2/8 (v/v) Inventive Nickel 1/2 0.5 1.0 FEC/MA Example 22 2/8 (v/v) Inventive Nickel 1/2 0.5 1.0 FEC/DMC Example 23 2/8 (v/v) Inventive Nickel 1/1 1.0 1.0 FEC/DMC Example 24 2/8 (v/v) Inventive Nickel 1/1 1.0 1.8 FEC/DMC Example 25 2/8 (v/v) Inventive Nickel 1/1 1.0 2.0 FEC/DMC Example 26 2/8 (v/v) Inventive Nickel 1/1 1.0 1.0 FEC/MA Example 27 2/8 (v/v) Inventive Nickel 1/1 1.0 1.0 FEC/DMC Example 28 2/8 (v/v) Inventive Nickel 1/4 0.25 1.0 FEC/DMC Example 29 2/8 (v/v) Inventive Nickel 1/4 0.25 1.8 FEC/DMC Example 30 2/8 (v/v) Inventive Nickel 1/4 0.25 2.0 FEC/DMC Example 31 2/8 (v/v) Inventive Nickel 1/4 0.25 1.0 FEC/MA Example 32 2/8 (v/v) Inventive Nickel 1/4 0.25 1.0 FEC/DMC Example 33 2/8 (v/v) Inventive Cobalt 1/2 0.5 1.0 FEC/DMC Example 34 2/8 (v/v) Inventive Cobalt 1/2 0.5 1.8 FEC/DMC Example 35 2/8 (v/v) Inventive Cobalt 1/2 0.5 2.0 FEC/DMC Example 36 2/8 (v/v) Inventive Cobalt 1/2 0.5 1.0 FEC/MA Example 37 2/8 (v/v) Inventive Cobalt 1/2 0.5 1.0 FEC/DMC Example 38 2/8 (v/v) Inventive Cobalt 1/1 1.0 1.0 FEC/DMC Example 39 2/8 (v/v) Inventive Cobalt 1/1 1.0 1.8 FEC/DMC Example 40 2/8 (v/v) Inventive Cobalt 1/1 1.0 2.0 FEC/DMC Example 41 2/8 (v/v) Inventive Cobalt 1/1 1.0 1.0 FEC/MA Example 42 2/8 (v/v) Inventive Cobalt 1/1 1.0 1.0 FEC/DMC Example 43 2/8 (v/v) Inventive Cobalt 1/4 0.25 1.0 FEC/DMC Example 44 2/8 (v/v) Inventive Cobalt 1/4 0.25 1.8 FEC/DMC Example 45 2/8 (v/v) Inventive Cobalt 1/4 0.25 2.0 FEC/DMC Example 46 2/8 (v/v) Inventive Cobalt 1/4 0.25 1.0 FEC/MA Example 47 2/8 (v/v) Inventive Cobalt 1/4 0.25 1.0 FEC/DMC Example 48 2/8 (v/v)

TABLE 2 Con- Initial Discharge centration discharge capacity of Lithium capacity retention Lithium salt mAh/g ratio at 20th salt (mol/l) 0.2° C. cycle (%) Comparative LiPF₆ 1.0 254.3 96.0 Example 1 Comparative LiPF₆ 1.0 254.6 95.3 Example 2 Inventive LiPF₆ 1.0 258.1 97.2 Example 1 Inventive LiPF₆ 1.0 258.9 96.8 Example 2 Inventive LiPF₆ 1.0 256.9 98.3 Example 3 Inventive LiPF₆ 1.0 260.9 98.4 Example 4 Inventive LiPF₆ 1.0 260.3 96.9 Example 5 Inventive LiFSI 1.0 260.5 97.1 Example 6 Inventive LiPF₆ 1.0 258.8 96.3 Example 7 Inventive LiPF₆ 1.0 262.3 97.7 Example 8 Inventive LiPF₆ 1.0 263.6 98.5 Example 9 Inventive LiPF₆ 1.0 258.4 98.1 Example 10 Inventive LiPF₆ 1.0 260.3 96.5 Example 11 Inventive LiFSI 1.0 260.5 96.9 Example 12 Inventive LiPF₆ 1.0 258.2 97.4 Example 13 Inventive LiPF₆ 1.0 259.1 96.9 Example 14 Inventive LiPF₆ 1.0 257.2 98.7 Example 15 Inventive LiPF₆ 1.0 261.3 98.5 Example 16 Inventive LiPF₆ 1.0 260.9 97.1 Example 17 Inventive LiFSI 1.0 261.4 97.4 Example 18 Inventive LiPF₆ 1.0 258.0 97.1 Example 19 Inventive LiPF₆ 1.0 256.9 98.2 Example 20 Inventive LiPF₆ 1.0 260.9 98.3 Example 21 Inventive LiPF₆ 1.0 260.1 96.4 Example 22 Inventive LiFSI 1.0 260.5 97.0 Example 23 Inventive LiPF₆ 1.0 258.8 96.3 Example 24 Inventive LiPF₆ 1.0 263.5 98.3 Example 25 Inventive LiPF₆ 1.0 258.6 98.1 Example 26 Inventive LiPF₆ 1.0 260.1 96.4 Example 27 Inventive LiFSI 1.0 260.1 96.8 Example 28 Inventive LiPF₆ 1.0 258.2 97.4 Example 29 Inventive LiPF₆ 1.0 257.2 98.5 Example 30 Inventive LiPF₆ 1.0 261.3 98.5 Example 31 Inventive LiPF₆ 1.0 260.9 96.9 Example 32 Inventive LiFSI 1.0 261.4 97.3 Example 33 Inventive LiPF₆ 1.0 258.1 97.2 Example 34 Inventive LiPF₆ 1.0 256.8 98.1 Example 35 Inventive LiPF₆ 1.0 260.3 98.4 Example 36 Inventive LiPF₆ 1.0 260.5 96.1 Example 37 Inventive LiFSI 1.0 260.4 97.1 Example 38 Inventive LiPF₆ 1.0 258.7 96.1 Example 39 Inventive LiPF₆ 1.0 263.3 98.2 Example 40 Inventive LiPF₆ 1.0 258.2 98.4 Example 41 Inventive LiPF₆ 1.0 260.3 96.3 Example 42 Inventive LiFSI 1.0 260.2 96.9 Example 43 Inventive LiPF₆ 1.0 258.4 97.2 Example 44 Inventive LiPF₆ 1.0 257.1 98.4 Example 45 Inventive LiPF₆ 1.0 261.6 98.3 Example 46 Inventive LiPF₆ 1.0 260.5 96.9 Example 47 Inventive LiFSI 1.0 261.6 97.2 Example 48

As is clear from the comparison of the inventive examples 1 to 48 to the comparative examples 1 to 2, if each of the particles containing the lithium composite oxide was coated with the coating layer containing an ammonium phosphate compound in the cathode active material, the decrease in the discharge capacity retention ratio was sufficiently suppressed in the secondary battery containing the cathode active material. In other words, the cycle characteristic was improved in the secondary battery containing the cathode active material. Furthermore, the secondary battery containing the cathode active material had a higher discharge capacity than the secondary battery containing a conventional cathode active material.

As is clear from Tables 1 to 2, the secondary battery containing the ammonium phosphate compound containing nickel or cobalt as the metal other than lithium had substantially the same cycle characteristic as the secondary battery containing the ammonium phosphate compound containing manganese as the metal other than the lithium.

INDUSTRIAL APPLICABILITY

The cathode active material according to the present disclosure can improve a cycle characteristic of a secondary battery. Therefore, the secondary battery containing the cathode active material according to the present disclosure is useful for various applications such as electronic devices such as mobile phones, smartphones, and tablet terminals, electric vehicles such as hybrid vehicles and plug-in hybrid vehicles, and home storage batteries combined with solar cells.

REFERENTIAL SIGNS LIST

-   1 Particle -   2 Coating layer -   10 Cathode active material -   11 Cathode -   12 Anode -   13 Separator -   14 Electrode group -   15 Case body -   16 Sealing body -   17, 18 Insulating plate -   19 Cathode lead -   20 Anode lead -   21 Recess portion -   22 Filter -   23 Lower valve body -   24 Insulation member -   25 Upper valve body -   26 Cap -   27 Gasket -   30 Cathode current collector -   31 Cathode mixture layer -   40 Anode current collector -   100 Secondary battery 

1. A cathode active material comprising: particles each containing a lithium composite oxide; and a coating layer containing an ammonium phosphate compound containing a metal other than lithium, wherein each of the particles is coated with the coating layer; and the metal other than the lithium includes at least one selected from the group consisting of manganese, nickel, and cobalt.
 2. The cathode active material according to claim 1, wherein a weight ratio of the ammonium phosphate compound to the lithium composite oxide is not less than 1.0 wt % and not more than 2.0 wt %.
 3. The cathode active material according to claim 1, wherein the lithium composite oxide includes at least one selected from the group consisting of nickel, cobalt, and manganese.
 4. The cathode active material according to claim 1, wherein the lithium composite oxide has a crystal structure which belongs to a space group R-3m or C2/m.
 5. A secondary battery, comprising: a cathode comprising the cathode active material according to claim 1; an anode comprising an anode active material capable of occluding and releasing lithium ions; and a non-aqueous electrolyte containing a non-aqueous solvent and a lithium salt which has been dissolved in the non-aqueous solvent.
 6. A secondary battery, comprising: a cathode containing a cathode mixture layer containing a cathode current collector and the cathode active material according to claim 1; an anode comprising an anode current collector; and a non-aqueous electrolyte containing a non-aqueous solvent and a lithium salt which has been dissolved in the non-aqueous solvent, wherein during charge, a lithium metal is deposited on the anode current collector; and during discharge, the lithium metal is dissolved in the non-aqueous electrolyte.
 7. The secondary battery according to claim 5, wherein the lithium salt contains at least one selected from the group consisting of LiBF₄, LiPF₆, LiN(SO₂CF₃)₂, LiN(SO₂F)₂, a lithium bis(oxalate) borate, and a lithium difluoro(oxalate) borate.
 8. The secondary battery according to claim 6, wherein the lithium salt contains at least one selected from the group consisting of LiBF₄, LiPF₆, LiN(SO₂CF₃)₂, LiN(SO₂F)₂, a lithium bis(oxalate) borate, and a lithium difluoro(oxalate) borate.
 9. The secondary battery according to claim 5, wherein the lithium salt in the non-aqueous electrolyte has a concentration of not less than 0.5 mol/L and not more than 3.5 mol/L.
 10. The secondary battery according to claim 6, wherein the lithium salt in the non-aqueous electrolyte has a concentration of not less than 0.5 mol/L and not more than 3.5 mol/L. 